GIFT  OF 


3^98 


THE     ESSENTIAL     OIL      OP 
SEQUOIA     SBMPERVIRENS 


A  thesis   submitted,  in  partial   satisfac- 
tion  of   the  requirements   for   the   degree 

of 
Master      of     Science 

at   the 

University  of  California 
by 

HAYWARD     1/JKRRIAM     SEVERANCE 


Berkeley,  Cal. 
April  1912 


(7 


IVk, 


Wu_. 


THE  ESSENTIAL   OIL   OF   SEQUOIA 
SEIIPERVIKEHS 


No  work  has  "been  done  on  this  oil,  so  far  as 
in  own,  with  the  exception  of  that  of  B.  H.  Eowrori, 
California  !02,  whose  results  were  presented  in  a 
thesis  for  the  "bachelor's  degree  April  1902.  So 
far  as  he  was  able  to  ascertain  "no  attempts  have 
teen  made  up  to  this  time  (1902)  to  investigate 
this  oil."  Ho  mention  of  it  has  "been  found,  in  the 
literature  since  that  date. 

The  Sequoia  genus  comprises  only  two  surviv- 
ing species;  (1)  the  Eigtree,  Sequoia  gigantea  Dec. 
(Washing ton! ana,  Y'ellingtoniaria)  growing  only  on  the 
western  slope  of  the  Sierra  Nevada  in  California; 
(2)  the  Kedwood,  Sequoia,  semp^rvirens,  growing  only 
in  a  narrow  "belt  along  the  Calif ornian  coasfc.  The  essen- 
ti- 1  oil  of  the  Eigtree  was  described  by  Lunge  and 
Steinkauler  in  1880  (Eerichte,  XIII,  1656  b,  XIV 
2202  b)  .  They  obtained  the  oil  from  small  trees  grow- 
ing in  Zurich,  Switzerland,  Their  results  are  dis- 

897057 


cussed  "below.  This  work,  quoted  "by  Gildemeister 

and  Hoffman,  is  the  only  one  found  on  the  oil  of  the 

Big tree. 

The  trees  used  in  this  work  (Redwood)  were 
all  young  growth,  largely  stump  sprouts  of  10  to 
20  years,  a,nd  were  cut  in  cut  over  forest  near 
Fort  Eragg,  I'endocino  co.,  Cal.  the  last  w«=ek  in 
February  1912.  A  previous  shipment  cut  during  a. 
personal  visit  to  the  woods  was  lost  in  transit. 
The  weather  conditions  here  (and  in  general  along 
the  coast)  are  a  temperature  of  about  50 °F  and  a 
moist  atmosphere  most  of  the  time.  During  the 
two  days  spent  at  Fort  Eragg  a  light  rain  fell 
almost  continuously.  This  may  have  been  pertly 
to  blame  for  the  rapid  loss  of  the  oil  from  the 
trees  after  cutting  end  during  storage  in  the 

basement  of ithe  Chemistry  Building  at  Berkeley. 

-^  . 

Apparatus --The  oi^  was  extracted  in  a  steam 
still,  shown  in  attached  print.  The  still  is  of 
copper,  the  upper  part  having  a  perforated  bot- 
tom on  which  the  material  extracted  rests.  The 
lower  part  contains  a  steam  coil  attached  to  the 
University  Lea ting  system.  Vater  is  poured  in  the 
lower  part,  heated  by  the  coil,  the  steam  generated 


passing  upward,  through  the  holes  in  the  plate  on 
which  the  material  rests.  In  starting  a  run  the 
water  was  also  heated  by  a  Bunsen  burner  un- 
til water  "began  to  come  through  the  condenser, 
after  which  the  steam  coil  furnished  heat  enough 
to  keep  a  small  stream  of  water  dripping  from 
the  outlet. 

The  four  joints  of  the  apparatus;  (l)  "be- 
tween the  top  of  the  still  and  the  head,  (2)  "be- 
tween the  two  parts  of  the  still,  (5')  "between 
head  and  cross  piece  and  (4)  "between  croespiece 
and  condenser,  were  all  packed  with  gaskets  cut 
from  asbestos  reinforced  with  fine  wire  mesh 
("gas  engine  packing11),  "between  brass  collars 
tightened  "by  "brass  screws.  The  lower  side  of  each 
ring  was  coated  with  white  lead  and  the  upper 
with  graphite.  This  did  away  with  the  necessity 
of  cutting  fresh  rings  after  each  run. 

At  the  start  of  each  run  the  still  was 
f illed.  with  w-.'ter  to  about  one  inch  in  the  gauge 
glass.  The  water  which  distilled  over  was  with- 
drawn from  under  the  oil  "by  a  siphon  and  returned 
to  the  still.  The  oil  floated  on  the  water  in 
the  receiving  bottle  and  was  withdrawn  from  time 
to  time  with  a  pipette.  In  some  cases  a  slight 


4 

additional   amount   of   oil   separated  from  the  milky 
water   in   the   large  "bottle   after    standing   overnight 
at   the  conclusion   of  a  run  and  was    also  withdrawn. 
The   oil  was   immediately  transferred  to   a  flask, 
kept   tightly  corked  in   the    dark  in   a  "basement  room. 

Yield--The   oil  as    it  came   over  had  a  golden 
Bellow  color   and  the   ocior   of   the  fresh  leaves.    It  « 
was  nearly  clear   "but  a  turbidity  developed  on 
standing. 

It  was   impossible   to  make   a  satisfactory,  deter- 
mination  of   the   yield  owing   to   several   circumstances. 
The   first   of   these  was   a   delay   of   a  week--ten   days 
after   cutting--bef ore   the   still  was   available. The 
first  run  was   interrupted  "by  a  leak   in   the   still 
p.tound  the  heating  coil,    causing  another   delay.    The 
solubility   of   the   oil    in  water  caused  a  consid- 
erable  loss,    especially   on   the  first  run. 

The   first  run  was   started  Harch  7.    Subsequent 
rugis  were  made  L'arch   20,    22,    26,    27,    s.nd  29,    and 
April   12.    The  rapid  decline   in  yield   -showed  that 
this  was    obviously  and  unfair    test.    The   odor  from 
the    trees  which  was  very  pronounced  e.t   frist,    de- 
clined proportionately   to   the   yield  and  appeared 
to   concentrate   lower    down   in   the  branchrs.    _s   the 


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5 

trees  "began  to  dry,  tlie  pleasant  aromatic  odor  dis- 
appeared, except  on  "breaking  a  twig  1-2"  or  more 
in  diameter,  and  another  quite  different  one  took 
its  place.  There  was  no  change  in  the  oil  except 
possible  slight  darkening.  (Owing  to  its  being 
spread  out  in  a  thin  layer  it  was  impossible  to 
determine  this. 

Blanches  were  cut  off  the  trees  as  needed, 
up  to  8,  diameter  of  about  -J-"  and  including  all 
of  the  growth  of  the  last  year.  The  terpene  odor 
was  strongest  in  the  tops  of  the  trees,  especially 
the  new  growth  of  the  main  trunk. 

The  still  was  packed  tightly  on  the  first  run 
with  7000  grams.  The  other  runs  were  made  on 
smaller  quantities  up  to  4600g.  with  the  idea  of 
hastening  the  time  of  extraction.  This  appeared 
to  be  complete  in  two  to  three  hours  in  all  cases 
except  the  first.  Y-Trien  this  work  is  resumed  a 
quantitative  determination  of  the  yield  from 
fresh  foliage  will  "be  made. 

Purification  of  the  oil--In  this  way  about 
150cc  of  oil  were  collected  (not  including  the 
oil  dissolved  in  the  water).  This  was  rectified 
. v  distillation  with  steam,  the  oil  coming  over 
being  collected  fractionally  in  four  portions 
of  about  25cc  each.  The  water  was  removed  by  a 


6 

separating  fuunel   and  the   oil   dried  "by  sodium 
sulphate.    The  first   fraction  after  "being  so 
treated  was  clear   and  colorless,   with  the   same 
odor   as   that   of   the   original   oil  but  more   del- 
icate—  evidently  a  terpene  hydrocarbon.    The   se- 
cond fraction  had  a  light  yellow  green   tinge, 
the   two  following  a  deeper  color.    After   four 
fractions  had  "been   collected,    the   oil   ceased  to 
co-iie   over  with   the  water   and  distillation  was 
stopped. 

Fractionation--The  first  fraction  was   dis- 
tilled again  from  a  20cc   flask.    (There  was  not 
enough  to  use   a  Hempel   column.)    The   oil    distilled 
almost  completely  at  157--160.    With  about  Ice  re- 
maining  the   thermometer   rose  above   162°  and  the 
residue   turned  greenish  yellow.    The   flame  was   re- 
moved at   this  point.    Ho   carbonization   or   decom- 
position was  evident   from  the   appearance   or    odor 
of   the  residue. 

The   second,    third,    and  fourth  fractions 
from  the   steam  distillation  were    distilled  a- 
gain.    The    distillate  was   collected  as   the   first 
fraction   to   160°,    the    second  to   1650.    The   tem- 
perature   then  rose  rapidly  to  190°   at  which 
most   of    the   remainder   passed  over.    This   fraction 


Je- 


7 

evidently  suffered  some  decomposition.  At  198° 
no  more  passed  over  and  the  temperature  dropped. 
The  residue  (about  2cc)  solidiifed  on  cooling. 
This  was  dissolved  with  ether  and  placed  in  a 
crystallizing  dish.  It  failed  to  crystallize, 
remaining  as  a  yellow  wax  with  slight  odor. 

The  first  fraction,  constituting  the 
greater  part  of  the  oil,  was  distilled  again 
and  constants  determined  as  follows; 

Boiling  point  157 °C  (Stem  exposed  above 
540) 

Specific  gravity  (capillary  pyvnometer) 

d     =  0.831 
150 

15° 


Refractive    index   (Abbe1)    n  —        1.473 

18.5° 


Polarization  (Schmidt  &  Haensch  polar- 

D 

iscope,  10cm  tube)  (a)     =  24°40' 

20°  " 

There  was  no  action  on  the  oil  "by  fresh- 
ly cut  sodium.  The  odor  resembles  that  of  the 
entire  oil  but  is  not  so  strong  and  each  dis- 
tillation appeared  to  diminish  it  slightly. 


8 

This   suggests   that   the   odor  may  come   from  a  trace 
of  high  boiling   aldehyde   or   ester. 

Ultimate   analysis — 0.3669g.    of   oil  was  burned 
in   a  combustion   analysis,    resulting   as   follows: 

Found  Calculated  for  ^IQ^-IQ 

C        87.085  88.20 

H        11.73  11.80 

The   low  yield  of   carbon   is   apparently  a  result 
of   the   large   quantity  taken   and  of   a  slightly 
rapid  current   of   oxygen   and  air   through   the   tube, 
causing   incomplete   absorption   of   the  COg.    To 
drive   off  all  moisture   in   the   tube    it  was  heated 
to   the   safe   limit   of  the  glass   for   an  hour   and 
cooled  with   a  slow  stream  of  purified  air  pass- 
ing  through. 

Comparison  with  terpene   from  Bigtree — Lunge 
and  Steinkauler  report   as   their   first   compound 
form  the   oil    of   Sequoia  washing t on iana  a  colorless 
oil,    b.    p.    155°,    d15o  0.8522;    vapor   density   (Vic- 
tor :>yer    in   diphenyl   amine)    69.67    (C10H16  ~  68) 

Rotation   (Wild  Polaristrobometer)    (a)..     23.8 

J 

Found  Calculated  G-^E^e 

C        86.09          87.90  88.20 

12.68  1230  11.80 


* 

. 


9 

-• 

. 


9 

Addition  of  Bromine — Two  cc  of  hydrocarbon 
were  dissolved  in  four  volumes  of  alcohol  and 
four  of  ether,  the  solution  cooled  by  ice  and 
sqlt  and  bromine  added  drop  "by  drop.  Complete 
discoloration  resulted,  indicating  unsaturation. 
Bromine  was  added  u#til  a  yellow  color  appeared. 
On  standing  in  ice  a  short  time  the  color  dis- 
appeared and  a  few  more  dops  of  bromine  were 
added,  shaking  after  each  addition.  When  the 
yellow  color  reappeared  the  tube  was  left  in 
ice  until  the  ice  melted  but  no  crystals  ap- 
peared. The  tube  was  then  exposed  to  the  air. 
After  approximately  a  third  of  the  solution  had 
evaporated  a  layer  with  a  slight  yellow  tint 
appeared  at  the  bottom.  At  room  temperature  this 
was  slightly  turbid,  but  cleared  on  warming  to 
about  25°.  After  three  days  the  solvent  was  driv- 
en off  as  much  as  possible  by  surrounding  with 
water  which  was  gradually  brought  to  boiling. 
There  still  remained  a  volume  of  solvent  approx- 
imately that  of  the  oil  below.  The  upper  layer 
was  pipetted  off,  some  of  the  lower  removed  and 
placed  in  a  clean  tube,  a  few  drops  of  ligroin 
added  and  the  tube  cooled  and  allowed  to  stand 
24  hours.  The  oil  again  separated  as  a  turbid 
liouid,  clearing  on  .»-;entl^  warming. 


10 

As  the  quantity  of  "brominated  oil  on  hand 
was  not  sufficient  to  attempt  a  purification  by 
distilling,  it  was  transferred  to  a  "boiling  point 
apparatus  and  the  sulphuric  acid  "bath  slowly 
heated.  The  oil  gradually  darkened,  indicating 
a  separation  of  "bromine.  At  50°  it  was  red 
(the  color  of  dilute  ferric  sulphocyanate) 
and  at  100°  almost  "black.  At  157 o  fumes  of 
bromine  and  hydrobromic  acid  came  off  co- 
piously and  the  oil  distilled  into  the  reser- 
voir above  the  air  chamber.  After  cooling  the 
liquid  remained  black,  slightly  more  viscous 
and  with  a  changed  odor,  but  not  one  suggesting 
carbonization. 

Addition  of  Iodine — About  Ice  of  oil  was 
dissolved  in  an  equal  volume  of  absolute  alcohol 
and  a  saturated  solution  of  iodine  in  alcohol 
added  drop  by  drop  with  shaking.  No  visible  dis- 
coloration followed.  The  mixture  was  allowed  to 
stand  for  two  days  and  the  excess  aloohl  was 
then  driven  off  by  immersing  the  bottle  in  water 
which  was  brought  to  a  boil.  The  liquid  which 
remained  had  a  color  not  quite  as  dark  as  ordin- 
ary iodine  tincture  and  a  peculiar  odor  resem- 
bling that  of  anethol.  Owing  to  lack  of  ti.,-.e 
work  was  discontinued  at  this  point.  _Ji  attempt 


11 

to  form  ;;n  iodine  addition  compound  will  "be  made 

later. 

Residue  of  the  original  oil — The  residue 
which  remained  in  the  flask  on  the  rectification 
by  distillation  with  steam  was  separated  from  the 
water  by  a  separating  funnel  and  allowed  to  stand 
£ntil  the  emulsion  layer  and  presumably  impurities 
carried  over  from  the  original  distillation  had 
settled.  This  left  a  yellow  oil,  thicker  than  the 
original  oil  s.s  obtained  from  the  still  and  with 
nearly  the  same  odor.  This  oil  was  filtered  through 
cotton,  coming  through  perfectly  clear.  On  heating 
it  was  found  to  contain  a  large  percentage  of 
water.  Granulated  calcium  chloride  was  added  and 
the  oil  allowed  to  stand  two  days  with  occasion  1 
shaking.  A  considerable  amount  of  water  separated 
out  below  the  oil.  An  attempt  was  then  made  to 
distill  the  oil.  This  was  a  total  failure  under 

Lospi-eric  pressure.  Decomposition  (and  prob- 
ably formation  of  resins)  occurred  before  any 
vapor  passed  over.  The  quantity  of  unheated  oil 
on  hand  was  not  sufficient  for  a  distillation 
under  reduced  pressure  and  that  is  also  deferred 


12 
pending  a  new  supply  of  foliage. 

Products  from  the  Bigtree — As  the  only  close- 
ly allied  botanical  species,  the  Sequoia  oils  give 
an  indication  of  possible  products  to  expect  from 
the  redwood.  Lunge  and  Steinkauler  report  the 
following,  "besides  the  hydrocarbon  already  re- 
ferred to: 

(2)  A  colorless  oil  turning  yellow  on  long 
keeping,  odor  reminding  of  peppermint.  Boiling 
point  227--2300,  d  1.045,  n  about  —60 

(3) In  very  small  amount  a  heavy  yellow  oil, 
boiling  point  280--2900. 

(4)  A  solid  body  "Sequojen"  with  melting 
point  105°,  boiling  point  290-300°.  White  leaf- 
lets with  weak  bluish  fluorescence. 


This  study  was  begun  at  the  suggestion  of 
llr.  Carl  A.  Kupfer,  Forest  Assistant,  United 
otates  Forest  Service,  San  Francisco,  to  whom 
a  indebted  for  kind  assist  ance  at  several 
stages  of  the  work.  Acknowledgments  are  also 
due  to  President  -Johnson  -nd  other  officers  of 
the  Union  Lumber  Co.,  S?n  Francisco,  for  assis- 


- 


o    e  tf  o.v 


rto   wo  Ile 


o 


tooei 


-8i 


13 

ance  in  securing  material  end  to  Dr.  G.  E.  Burke 
of  the  College  of  Chemistry,  University  of  Cal- 
ifornia for  many  suggestions  and  aids  in  the  an- 
is.  To  all  of  these,  my  most  cordial  thanks. 
The  work  will  "be  continued. 


Chemistry  Building,  University  of  California, 

Berkeley,  Cal. , 
April,  '1912. 


Sprout  grovrbh  from  Bed  ;  od  stunp. 
Material  of  c"      r  used  in  this  v/orl:. 
:ioto  by  Forest  Service 


NON-CIRCULATING  BOOK 


U.C.BERKELEY  LIBRARIES 


297057 


UNIVERSITY  OF  CALIFORNIA  LIBRARY 


